Aliphatic polyether polyamides



Patented Oct. 3, 1944 2,359.70}; surname romrrnna, rommmnss Herman A. Bruson, Philadelphia, Pa... assignor to The Resinous Products & Chemical Company,

Philadelphia, Pa., a corporation of Delaware No Drawing. Application April 4, 1942, Serial No. 437,679

eciaims. (01.260-561) a This invention relates to aliphatic polyether polyamides having the formulawherein A is the-nonehydroxylated organic residue of an aliphatic polyhydric alcohol having from 2 to 6 (inclusive). hydroxyl groups per molecule, and n is an integer from 2 to 6 inclusive.

These compounds are obtained according to this invention by partial hydrolysis of the correspending aliphatic polyether polynitriles of the formula- A(OCH2CH2CN) dric alcohol, corresponding to A in the above general formulae, is an acyclic hydrocarbon chain or an acyclic hydrocarbon chain which is interrupted by oxygen or sulfur to form alkylene where A and n have the above-mentioned $18 niflcance. These polynitriles in turn are'obtained by reacting aliphatic polyhydric alcohols having 2 to 6 hydroxyl groups in the molecule with acrylonitrile in the presence of an alkaline condensing agent, such as sodium or potassium hydroxide, sodium methylate, a quaternary ammonium hydroxide, etc., according to the method described in ccpending application Serial No. 374,603, filed January 15, 1941, of which the present application is a continuation-in-part. In said application it is shownthat polyhydric alcohols, such as ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene, glycol, pentamethylene glycol, octamethylene glycol, decamethylene glycol, octadecanediol, divinyl glycol, dipropenyl glycol. Glycerol, trimethylol propane-1,1,1, butantriol-2,8,e, pentaglycerol, erythritol, pentaerythrite, mannitol, sorbitol, diethylene glycol, dipropylne glycol, triethylene glycol, thiodiethylene glycol, thiotetraetlwlene glycol, hexaethylene glycol, nonaethylene glycol, higher polyethylene glycols having molecular weights up to 4000, or other aliphatic polyhydric alcohols are reacted with acrylonitrile in the presence of an alkaline catalyst toiorm poly-p-cyanoethyl ethers of the po yhydric alcohols.

Typical poly-p-cyanoethyl ethers are shown in the following list NC-CHICHr-O-CHiCHPO-CHsCHzCN NC Cecee? easements NC-CHrCHr-(Q-CHaCH2):OCH:CH:CN

- (where z is 3 or more) r-O-CHaCHaCN (where x is 3 or more)- It will be noted that the non-hydroxylated orchains ofat least two carbon atoms each between the oxygen or sulfur atoms. I

The partial hydrolysis of such polycyanoethyl others is carried out in the presence of sulfuric acid of at least 80% strength' There must be present at least one mol of water for each nitrile group to be hydrolyzed. In general the best results are obtained when one equivalent of both water and acid are present for each cyano group to be hydrolyzed; The hydrolysis is performed at to 100 C. Higher temperatures cause fission at the ether linkages. When the reaction has been carried to the formation of polyamide, the sulfuric acidis neutralized and the polyamide separated.

In view ofthe proclivity of sulfuric acid to split ethers, it is a surprising result that good yields of ether polyamides are thus obtained. In thiseonnection it is of interest to note that in 'hydrolyzing the polyether polynitriles, amide formation by strong aqueous alkalies is not feasible, as they cause fission of the molecule at the ether linkages. 1

The polyether polyamides obtained ar new mol) was added dropwise during 1% hours to 84 parts (0.5 mol) of di-(p-cyanoethoxyhethane NCCH:CHaOCH2CH2OCH:CHzCN while the reaction mixture was stirred and maintained at C. The mixture was then heated for five hours at 70 C., cooled, and neutralized with 25% sodium hydroxide solution at 10-20 C. The solution was cooled to 10 C. and filtered to remove the sodium sulfate. The filtrate was evaporated to dryness on a steam bath at -95 C. under reduced pressure. A 'syrupy residue was obtained which crystalized on standing. It was recrystallized from dioxane to yield a product (56 parts), which separated in colorless needles, having a melting point of 123-124" C. having the formula-.

HINO CCHxCH:O-C HaCHr-O-CHaCHzC ONE:

and being verysoluble in water, but only slightly soluble in cold acetone or dioxane. The di-(p-cyanoethoxy) -ethane used above is' a colorless liquid B. 1?. 158/2 mm., obtained by tion.

Example 2.-A solution of 200 parts of 98% sulfuric acid (2 mols) and 36 parts of weter fs,

(2 mols) was added dropwise during two hours to 212 parts (1 mol) of bis-fi,p-(2-cyanoethpm) diethyl ether.

NC-CHaCHr-O-CHsOHr-O-OHsCHr-O-OHgOHaCN while the reaction mixture was stirred and maintained at 65-'75 C. The mixture vwas then stirred and heated at 70 C. for six hours. It was cooled to 10 C. and neutralized dropwise with a 25% sodium hydroxide solution while the temperature was kept below 20 C. The neutral solution was cooled to 8 C. and the sodium sulfate crystals filtered oil. The filtrate was freed from water at 90 C. under reduced pressure, leaving a syrupy residue containing some sodium sulfate. The latter was removed by hot vacuum filtration and the filtrate heated with dioxan When the'filtered dioxane solution was cooled, the product separated in colorless crystals in a yield of 165 parts. The compound was purified by recrystallization from dioxane and melted when pure at 103-104. It has the formularnNo Q:CH|CHrO-CHsCHn-O-CHaCHg-O-CHsCHsC ONE:

It is very soluble in water.

Example 3.--A solution of 200 parts of 98% sulfuric acid (2 mols) and 36 parts (2 mols) of water was added dropwise to 174 parts (0.5 mol) of tetraqs cyanoethoxymethyl) methane at 70-'l8 C. during one hour with constant swarm The mixture was then held at 75 C. for 5 hours. It was then cooled to 15 C. and neutralized by the gradual addition of 25% caustic soda solution under such conditions that the temperature did not exceed 20 C. The product was filtered to 40 remove sodium sulfate and the latter washed with 200 parts of ice water. The combined washings and filtrate were evaporated to dryness in vacuo on a steam bath and the colorless syrup obtained was dissolved in absolute ethanol and filtered to remove traces of salts. Upon removal of the alcohol by evaporation under reduced pressure, 180 parts of product consisting essentially of tetra(s-carbamylethoxy methyl) -methane HsNOC CHaCHr-O-CH:\ /CHPOCHQCHIC ONE:

HzNOCCHsCHg-O-CH: CHr-O-OHaCHaC ONE! was obtained as a pale resinous water-soluble mass.

In the same manner other polyether polynitriles of the formula A(OCH:CH:CN). as

described above, can be converted to the corresponding polyamides without scission oi the ether linkage.

I claim: 1. A method for preparing aliphatic polyether polyamides having the formula A 0omcH,-ooNm).

wherein A is the non-hydroxyl portion of an allphatic po yhydric alcohol having from 2 to 6 (inclusive) hydroxyl groups, and n is an integer from 2 to 6 inclusive, which comprises reacting between C. and 100 C. an aliphatic polyether polynitrile having the formula o-omcmom.

wherein A and n have the above mentioned significance, with one molecular equivalent each of sulfuric acid and water for each cyano group present in the molecule and neutralizing the reaction mixture with alkali.

2. As a new compound, an aliphatic polyether polyamide having the formula wherein A is the non-hydroxyl portion or a polyhydric aliphatic alcohol having from 2 to 0 (inclusive) hydroxyl groups, and n is an integer from 2 to 6 inclusive.

3. As a new compound, 1,2-di-(p-carbamyle ethoxy) ethanehaving the formula 0 the reaction mixture was maintained at -75 C.

4. As a new compound 2,2'-di-(s-carbamylethoxy) -diethyl ether having the formula HsNO C-CH:CHs-O-OH:OHrO-CHaCHs-O-CHsUHl-O ONE:

5. As a new compound tetra-(p-carbamylethoxymethyl) -methane having the formula 6. As a new compound, an aliphatic polyether polyamide having the formula to ninety.

HERMAN A. BRUBON. 

